THE GASEOUS STATE

PRESSURE
1 atm = 101,325 Pa = 101 kPa

BOYLES LAW
At constant temperature, the volume of a fixed mass of gas is inversely proportional to its pressure.
V=k

, where k is a constant.
OR

pV = constant and P1V1 = P2V2 when temperature is constant.

CHARLES LAW
At constant pressure, the volume of a fixed mass of gas is directly proportional to its absolute
temperature.
V = mT, where m is a constant.
OR

= constant and

when pressure is constant.

AVOGADROS LAW
At any given temperature and pressure, the volume of a gas is directly proportional to the number of
molecules present.
V = k n, where k is a constant.
OR

= constant and

when temperature and pressure are constant.

COMBINED GAS EQUATION

IDEAL GAS
An ideal gas is a hypothetical gas whose pressure volume temperature behaviour can be
completely accounted for by the ideal gas equation pV = nRT.
pV = nRT

T must always be expressed in Kelvin.

n is usually expressed in moles.
R = 8.31 J K-1 mol-1
1 cm3 = 1 10-6 m3
1 dm3 = 1 10-3 m3

GAS MIXTURES & PARTIAL PRESSUES

In a mixture of gases, the pressure exerted by any individual gas on the sides of a container is known
as the partial pressure of the gas.
Daltons law of partial pressure states that the total pressure of a mixture of gases is the sum of
the partial pressure of the constituent gases.
Ptotal = PA + PB + Pc

()

Pa = ( ()) Ptotal
where

()
()

is called the mole fraction.

In a gas mixture, the partial pressure of any individual gas is proportional to its mole fraction in the
mixture.
In a mixture of gases, the amount (or number of moles) of any individual gas in proportion to the
total amount of gas is called its mole fraction.

KINETIC MOLECULAR THEORY OF GASES

The kinetic molecular theory is based on the following assumptions, as applied to an ideal gas whose
particles are in continuous, random motion:
1. Gas particles behave as rigid spheres.
2. The size of the gas particles is so small compared to the space between them that we can
assume that the particles themselves have negligible volume. The gas particles have
negligible volume compared to the volume of their container.
3. The intermolecular forces between gas particles are negligible.
2

4. Collision between gas particles, and their collisions with the walls of the container, are
perfectly elastic; there is no net loss or gain of kinetic energy during collision.
5. The average kinetic energy of the gas particles is directly proportional to the absolute
temperature. So at a particular temperature, all types of gaseous particles have the same
average kinetic energy.

MAXWELL-BOLTZMANN DISTRIBUTION CURVE

Although collectively the molecules in a gas sample have the same average kinetic energy,
the individual molecules are moving at different speeds.
At a given temperature heavier gases travel slower while lighter gases travel faster.

(KE=mv2)

Given a gas sample at different temperatures, the speed distribution of the molecules shifts
toward higher speeds and becomes less sharply peaked as the temperature (and kinetic
energy) of the gas sample is increased.
Even at low temperatures, there is small number of molecules having high speed and kinetic
energy. This number of molecules increases with temperature, while the number of
molecules with low speed and KE becomes smaller but does not vanish.
3

Important features:
1. Graph would have the same shape when either speed or kinetic energy is used as the x-axis.
2. Labels for vertical (y) axis include number of (gas) particles (or molecules), proportion of
particles, or fraction of particles.
3. The area under the curve generally represents the total number of particles in the sample.
For a fixed sample and different temperatures, the area should remain the same even
when the curve shifts.
4. The peak of each curve represents the most probable speed (or KE). As the temperature
increases, the peak decreases in height and shifts to the right as the distribution of
molecular speeds becomes more spread out.
5. All curves start at the origin (0,0) because in a gas sample there are no particles with zero
speed (or KE) and all particles must be moving.
6. The curves do not show a maximum speed (or KE) value. The curves do not intersect the
x-axis again as there is theoretically no limit to the amount of speed (or KE) a particle can
have.

DEVIATION FROM IDEAL BEHAVIOUR

In practice, a real gas behave almost like an ideal gas and obeys the ideal gas equation
closely and under the following conditions:
At Low Pressure

At low pressure, the gas molecules are

relatively far apart.
Intermolecular forces are negligible
and observed pressure is close to that
predicted by the ideal gas equation.

At High Temperature

At high temperature, the gas

molecules possess sufficiently high
kinetic energy to overcome the
intermolecular
attractive
forces.
Hence the intermolecular forces are
considered negligible.

The volume of the molecules

themselves is negligible compared to
the volume of the container. Real gas
molecules a low pressure can be
approximated to have negligible
molecular size, and their behaviour
would approach that of an ideal gas.

Conversely, a real gas behaves least like an ideal gas under the following conditions
At High Pressure

At high pressures, intermolecular

distances become shorter and
intermolecular forces become more
significant. This lowers the impact of
molecules colliding the container
wall. Thus the observed pressure is
less than that expected of an ideal
gas.

The molecules take up a large portion

of the volume of the container,
resulting in a considerably smaller
space in which the molecules can
move. Thus it is no longer valid to
assume that molecular size is
negligible, as the total volume
occupied by a real gas is actually
greater than the volume predicted by
the ideal gas equation.

At Low Temperature

The kinetic energy of the gas particles

decreases and this causes them to
move more slowly and intermolecular
forces become more significant. This
also causes the collision to be inelastic.
Eventually, it reaches a point where
the particles can no longer overcome
the intermolecular attractive forces,
at which point real gases liquefy
(condense to form a liquid).

Comparing the Behaviour of Different Real Gases

Large molecules, which have large electron clouds, occupy more space and have stronger
intermolecular forces between molecules, Hence they deviate more from ideal behaviour
than molecules of smaller size.
Polar molecules tend to have stronger intermolecular forces of attraction (e.g. permanent
diploe permanent dipole interactions or hydrogen bonding). Hence they would deviate
more from ideal behaviour than non-polar molecules of similar size.

MISCONCEPTIONS & REMARKS

When water (or other molecule) boils, take note that the number of gaseous particles
increases and this in turn increases pressure (if the container is enclosed). [T4 Q1]
When the question states "explain in terms of the behaviour of gas molecules" or
"explain in molecular terms", you are not allowed to explain using the pV=nRT equation.
[T4 Q1]
Note that average kinetic energy is constant as long as the temperature is constant.
Do not state that ideal gases have negligible volume compared to the container, the
correct statement is that particles of ideal gases have negligible volume compared to the
container or molecular volume of the gas is insignificant with respect to the volume of
the container [T4 Q1]
For an ideal gas, the volume of the container is the volume of the gas.
When a gas dimerizes completely, the number of moles decreases by half.
Note a constant temperature, pV = constant if the gas behaves ideally. [Class Test Q1]
Accounting for the discrepancies in the volume occupied by gas under high pressure: Under
conditions of high pressure, significant IMF (depends on different gases) exist between the
gas molecules. Hence they are pulled closer together, which causes the actual volume of the
gas to be smaller than that predicted by ideal gas equation. [Class Test Q1]
Note if 2 or more variables are constant throughout the question, e.g. volume and constant
R, it is possible to combine them into a single constant. E.g.

= k [TP4 Section B Q5]

For

to infinity, hence pV will NOT approach 0 (but 1). [TP4 Section A Q15]
At a given temperature heavier gases travel slower while lighter gases travel faster.

(compressibility factor of one mole of any real gas), when p approaches 0, v increases

(KE= mv2) but their average kinetic energy are the same.

[2012 BT1 Paper 1 Q17]

Take note of the number of atoms as well as the type of atoms in a molecule in determining
its electron cloud size. CO2 has a bigger electron cloud than O2. Take note that there is an
additional C atom is carbon dioxide, and hence the dispersion forces in carbon dioxide is
stronger and it deviates more from an ideal gas. [2012 BT1 Paper 3 Q2]
When a higher pressure is applied, the gas molecules are forced closer together, and the
intermolecular forces becomes more significant. [2013 BT1 Paper 3 Q1]